Note: Descriptions are shown in the official language in which they were submitted.
2i5i~41
FIELD OF INVENTION
The present invention relates to a method of
decolorizing alkylated diarylamine antioxidants, made
using aluminum halide catalyst, by treating the
diarylamine with clay.
BACKGROUND
Alkylated diarylamines are known antioxidant
compositions used as stabilizers in organic materials.
Typically, these alkylated diarylamines are made by
reacting an olefinic compound with diphenylamine in the
presence of aluminum chloride catalyst. The resulting
compounds are deeply colored, possibly due to strong
activity of the catalyst or a reaction between the amine
and the chloride. Such colored products have less appeal
in the industry because certain antioxidant utilities
require a high degree of purity or absence of colored
contaminants, or simply because dark colored antioxidants
are aesthetically less appealing.
Distillation may improve the color but often
it is not enough since coloration reoccurs through
oxidation of remaining contaminants. Therefore, it is
desirable to find an adsorbent which can specifically
remove the color contaminants generated from aluminum
halide catalyst alkylation of diarylamines. Heretofore,
decolorization of various amines required special
adsorbents such as zinc, as disclosed in Reagents for
Organic Synthesis, Vol. l, p. 1281, Fiester & Fiester,
1967, bromine as disclosed in Derwent Abstract
117:25931b, page 649, Vol. 117, 1992, or ion-exchange
resins, as disclosed in U.S. 5,097,041. Carbons, molecular
215~p4~
sieves and silica gel which are common adsorbents for
color contaminants as taught by Kirk-Othmer, Encyclopedia
of Chemical Technolocty, 3rd ed., Vol. 1, p. 532 (1978),
do not work well at all. Clays are known decolorizers for
vegetable, animal and petroleum oils, but are not known
for amines.
US-A-2,833,824 teaches a method for purifying
N,N'-diphenyl-p-phenylenediamine but does not teach de-
colorization of alkylated diphenylamines.
U.S. Patent No. 4,824,601 discloses the use of
activated earth catalysts to produce alkylated
diphenylamine liquid antioxidant compositions lighter in
color than those obtained using aluminum chloride
catalyst. Additionally, to achieve bleaching and
alkylation using clay catalyst, the reaction must occur
at a relatively high temperature, 160°C or higher, which
is not practical. Also, clay is a substantially less
effective catalyst than aluminum chloride in that under
equal conditions, substantially less diphenylamine is
converted into product by clay as compared to aluminum
chloride. This is demonstrated in Example 2 following
herein. Therefore, it is more desirable to produce the
alkylated diphenylamines using aluminum chloride
catalyst. A new method of removing the color contaminants
produced specifically from aluminum halide catalyzed
alkylation of diarylamines has been discovered. The
instant inventive method will enable the industry to
utilize efficiently produced diarylamine antioxidant and
subsequently decolorize it by a simple, efficient method
of mixing and heating clay with the colorized
antioxidants.
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SUMMARY OF THE INVENTION
The present invention pertains to a method for
decolorizing alkylated diarylamines, said method being
characterized by:
a) contacting one or more alkylated diarylamines with
clay surfaces, said alkylated diarylamines being the
reaction product of one or more olefinic compounds and
one or more diarylamines in the presence of aluminum
chloride and having colored contaminants;
b) allowing said colored contaminants to associate
with said clay surfaces; and
c) separating said alkylated diarylamines from said
clay surfaces.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a method for decolorizing
alkylated diarylamines, said method comprising; (a)
mixing a colored alkylated diarylamine with clay to
produce a mixture; (b) heating said mixture; and (c)
separating said clay from said alkylated diarylamine.
Any colored alkylated diarylamine can be decolorized by
the present method. Diarylamines are known in the art
and art described in Volume 2, pages 329-337 of Kirk-
Othmer, Encyclopedia of Chemical Technology, 3rd ed.,
1978. One skilled in the art, however, will appreciate
that colored alkylated diarylamines requiring
decolorization typically will be those made using
aluminum halide catalyst, namely aluminum chloride.
Suitable alkylated diarylamines include, but are not
A
21510~I
limited to those from diphenylamines; N-phenyl-
naphthylamines; and phenothiazines, etc. For example,
suitable alkylated diphenylamines include those having
the following general formula:
R1 ~ R3
N
R2 R4
wherein
R1, R2, R3 and R4 independently are H,
branched, or straight-chain C1-C1z alkyl radicals, benzyl
group or a straight chain C1-C4 alkyl benzyl group.
Accordingly, suitable diphenylamines include
but are not limited to, p,p'-dioctyl-diphenylamine; p,p'-
dinonyl diphenylamine; p,p'-di-a-methylbenzyl diphenyl-
amine; o,o'-diethyl-p, p'-dinonyldiphenylamine; and o,o'-
diethyl-p, p'-di-a-methylbenzyl diphenylamine. Those
skilled in the art will appreciate that the diarylamine
may consist of a physical blend of more than one
diarylamine, such as one comprising a blend of p,p'-
di(butyl and/or octyl) diphenylamine; p-(butyl or octyl
diphenylamine; p-tert-butyl-p'-tert-octyl-diphenylamine
and diphenylamine or the blend from the reaction of
diphenylamine and a mixture of diisobutylene and styrene.
Also included are derivatized alkylated diaryl-
amines obtained from further reaction, such as the ones
taught by U.S. 5,634,248 from the reaction of alkylated
diarylamine, with aldehyde, or the ones taught by U.S.
3,509,214 and 3,573,206 from the oxidation of diaryl-
A
~ 1 ~ 104~~
amines, or the one taught by U.S. 3,492,233 from the
dehydrocondensation of diarylamines and a lubricant, or
the ones taught by U.S. 3,539,515 regarding peroxide-
treated phenothiazines as an antioxidant.
Any clay, most of which are aluminosilicates,
having decolorizing capacity is suitable. Conventional
clays used for decolorization of mineral, vegetable and
animal oils are suitable in the present inventive method.
This includes a wide range of clay materials from fine-
grained silts to clays composed of almost pure clay
minerals. Crude clay, also known as Fuller's earth, is
suitable. The preferred clays are those which have been
acid treated, such as Fulcat~ sulfuric acid-activated
Fuller's earth, commercially available from Laporte
Industries. A particular suitable clay is bentonite
acid-bleached clay known as FiltrolTM or RetrolTM grade
clay. It is approximately 97°s by weight aluminum silicate
and approximately 1-3°s crystalline silica. It is
commercially available from Englehard Corporation,
Jackson, Mississippi, U.S.A, as product Grade F-6 or
Grade F-13. Other suitable clays will include mont-
morillonite, halloysite, and sepiolite and those composed
of attapulgite.
In the method of the present invention, the
alkylated diarylamine is mixed with the clay using
conventional means for a sufficient time to allow for
decolorization of the diarylamine. Typically, between 5-
45 minutes mixing time is sufficient. Typically, the
mixture will be thick and therefore heating the mixture
will be advantageous. Best results are obtained when the
mixture is heated to at least 50°C. Although it is
_6_ 2151041
suitable to heat the mixture beyond 150°C, one skilled in
the art will appreciate that it is more efficient to keep
the temperature below 150°C. Desirably, the temperature at
which the mixture is mixed will be from about 70°C to
150°C, preferably between 80°C to 130°C, and most
desirably between about 90°C to about 120°C and optionally
to 150°C. The amount of clay necessary to decolorize the
diarylamine is not critical although at least 0.5% by
weight, based on the total weight of the diarylamine
desirably will be used. Generally, the more clay used,
the better the results achieved. A suitable range is
between 2% and 10% clay. The decolorized antioxidant
alkylated diarylamine can be separated from the clay
using any conventional method, especially filtration and
preferably while the mixture is hot.
A further method of decolorizing
diarylamines is by contacting of the diarylamine with
clay surfaces, allowing the colored species to be
associated as by absorption or adsorption (i.e. sorbed)
by the clay and physically separating (as by filtration
or otherwise isolating) the less colored diarylamines
from the clay combined with the sorbed colored species.
One way to contact the clay with the diarylamines is to
form a packed column with the clay or use the clay as
part of a filter media or filter bed. This method makes
use of the fine particle size and high surface area of
the available clay products. The temperature of the clay
and/or the diarylamine may be increased above ambient as
described above to decrease the viscosity of the
diarylamine allowing shorter filtration times or higher
throughput. The throughput of diarylamine may also be
h
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increased by using an apparatus capable of being
pressurized on the input side of the filter or capable of
maintaining below atmospheric pressure on the output side
of the filter. Other methods of achieving high surface
contact between solids and liquids may also be used with
appropriate adjustments for the physical characteristics
of the diarylamines and the available clay-based
products. These may include things such as fluidized beds
or the use of clay supported on an inert support medium
or structure.
The colored alkylated diarylamine may be one
which has been already treated by another means of
decolorizing such as distillation. If the equipment for
decolorization can handle the alkylated diarylamine,at
ambient temperatures (i.e., 20-30°C) then heating is not a
necessary step.
SPECIFIC EMBODIMENTS
The following nonlimiting examples will
provide the reader with a more detailed understanding of
the invention.
EXAMPLE 1
A liquid antioxidant consisting of p,p'-
di(butyl/octyl) diphenylamine; p-(butyl/octyl) diphenyl-
amine; p-tert-butyl-p'-tert-octyl-diphenylamine; and
diphenylamine was placed in a flask. RetrolTM, a clay
from Mississippi was added in the amount of about 10% of
the weight of the antioxidant. They were mixed and
stirred at 120°C for 30 minutes, then filtered while hot
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through a fritted funnel. The decolorized oil had a
reading of < 0.5 - 1.0 on the Fisher Scientific ASTM
D1500 Colorimeter compared to a number >8 before the
process. Use of carbons, silica gel or molecular sieves
gave a color measurement of between 3.5-6.
EXAMPLE 2
To show the A1C13 is a much stronger catalyst
than clay, 1 mole diphenylamine and 3 mole diisobutylene
with 4% A1C13 (based upon the weight of diphenylamine)
were refluxed at 105-110°C for two hours, 85% of the
diphenylamine was converted into a mixture 3:2 mono- and
di-octylated diphenylamine. While under the same
condition, the 4% A1C13 was replaced by 4% Retrol'M and
only < 5% of the diphenylamine was converted to mono-
octylated diphenylamine.
EXAMPLE 3
The same blend ofalkylated diphenylamines
as in Example 1 was treated with 5% RetrolTM at 100°C for
15 minutes, followed by distillation at 666/6 Pa (5mm Hg)
vacuum to afford a light-colored oil with a color reading
of <0.5.
EXAMPLE 4
A distilled blend of alkylated
diphenylamines made from an aluminum chloride catalyzed
reaction of diphenylamine and a mixture of diisobutylene
and styrene was decolorized by 5% FiltrolTM at 110°C for 10
minutes. The color went from >8 to 1-1.5.
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t, 2151 Q41
EXAMPLE 5
A 200 grams of undistilled blend of the same
alkylated diphenylamines as described in Example 4 was
warmed to 160°C and passed through a 5 gram bed of
TM
Filtrol grade 20 packed in a 150m1 fritted Buchner
funnel with pores sizes of 40-60 micrometers. A water
aspirator was used to supply vacuum to the receiver side
of the Buchner funnel. The color dropped from >8 to 3.
EXAMPLE 6
A crude product of aluminum catalyzed
reaction of diphenylamine an a mixture of diisobutylene
and styrene was passed through the medium of Example 5.
The crude product was the same crude product that. was
first distilled in Example 4 and contained some residual
diphenylamine, diisobutylene, and styrene. Then the
filtrate was distilled. The final color was between 3 and
3.5.
EXAMPLE 7
The same blend of alkylated diphenylamines
as in Example 1 was passed through a chromatograph column
TM
packed with 5% Filtrol grade 6. The color went from >8
to 2.5.
